CN105330776B - The method for preparing halogenated butyl rubber - Google Patents
The method for preparing halogenated butyl rubber Download PDFInfo
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- CN105330776B CN105330776B CN201410267111.9A CN201410267111A CN105330776B CN 105330776 B CN105330776 B CN 105330776B CN 201410267111 A CN201410267111 A CN 201410267111A CN 105330776 B CN105330776 B CN 105330776B
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Abstract
The present invention relates to a kind of method for preparing halogenated butyl rubber, including：A) solution comprising butyl rubber is reacted with halide reagent, obtain halogenated butyl rubber solution；And b) the obtained halogenated butyl rubber solutions of step a) are post-processed, to reclaim halogenated butyl rubber, wherein step a) halogenation is carried out in the presence of the optionally water containing emulsifying agent, and the mole ratio of the primary bit architecture in gained halogenated butyl rubber and secondary bit architecture is not higher than 1:10, following formula type III and II types represent primary bit architecture and secondary bit architecture respectively, and X represents halogen in formula.In addition, compared to conventional method, the halogenated butyl rubber that the inventive method obtains has the primary bit architecture of minor proportion, so that butyl rubber palliating degradation degree caused by halogenation reduces.Moreover, it relates to the optional purposes of the mol ratio of primary bit architecture and secondary bit architecture in halogenated butyl rubber is reduced of the water containing emulsifying agent.
Description
The present invention relates to a kind of method for preparing halogenated butyl rubber.Have in the halogenated butyl rubber prepared by this method
The ratio of the primary bit architecture of primary halogen atom is relatively low.The invention further relates to purposes of the water in this kind of halogenated butyl rubber is prepared, water
Presence can reduce the primary bit architecture containing primary halogen atom in halogenated butyl rubber and rubbed with containing the secondary bit architecture of secondary halogen atom
That ratio.
A kind of synthetic rubber that butyl rubber forms for isobutene with a small amount of isoprene copolymer, abbreviation IIR.Due to isoamyl
The amount of diene is considerably less than isobutene, therefore each isoprene monomer unit in butyl rubber is mainly with both ends and isobutene
The form of monomeric unit connection is present.It is generally believed that in apolar medium under the conditions of lucifuge, the bromination reaction of butyl rubber
It is a kind of ionic substitution reaction, its reaction mechanism mechanism of reaction is as follows：
It is raw after the isoprene unit (I types structure) in butyl rubber main chain contacts with bromine in the above-mentioned reaction mechanism mechanism of reaction
Into a bromineIonic intermediate.Due to bromineThe presence of the ion both ends tert-butyl group, the final product of this reaction mainly take
For structure (R.Vukov., Rubber Chemistry and Technology, 1984, Vol (57), P275-283).Also
It is that on isoprene unit a allylic hydrogen is substituted to obtain brombutyl by bromine atoms, while generates a molecule
Accessory substance HBr.Substitution structure have two kinds of primary structures according to the difference of halogen atom relative position, be respectively secondary bit architecture (II types) and
Primary bit architecture (type III).In general, after halogenating butyl rubber, the primary structure of halogenated products is secondary bit architecture.Due to uncle position
Structure is more stable relative to secondary bit architecture, and therefore, in halogenating butyl rubber course of reaction, some secondary bit architecture can isomery
Turn to primary bit architecture.In the presence of temperature rise and lewis acid, transition metal ions, the relative amount of primary bit architecture has rise
Trend.USP4,649,178 and USP4,632,963 is just disclosed by high temperature, lewis acid catalyst to prepare tool
There is the method for the brombutyl of high type III content.But in above-mentioned processing procedure, either heat treatment or addition road
Lewis acid class catalyst, all inevitably along with the degraded of polymer while type III structural content increase.It is actual
On, during butyl rubber bromination, inherently a kind of isomerization catalysts of accessory substance HBr.With the increase in reaction time, in product
Type III structural content increase, the serious degraded of simultaneous.
Exactly because different degrees of dehalogenation is accompanied by during the relative amount of primary bit architecture is increased, degrades and makes
Product quality declines, therefore in the industrial production, it is necessary to which reducing has the primary of primary halogen atom in halogenated butyl rubber product as far as possible
The content of bit architecture.
The content of the invention
In view of above-mentioned condition of the prior art, the present inventor carried out in halogenated butyl rubber field deeply and
Extensive research again, to find a kind of primary bit architecture content control that primary halogen atom can will be effectively included in halogenated butyl rubber
Make the halogenating butyl rubber method in reduced levels.As a result find, when the halogenation of butyl rubber solution and halide reagent exists
When optionally being carried out in the presence of the water containing emulsifying agent, it can substantially suppress the secondary position for including secondary halogen atom in halogenated butyl rubber
Structural isomerism is melted into the primary bit architecture for including primary halogen atom, former comprising primary halogen in gained halogenated butyl rubber so as to substantially reduce
The content of the primary bit architecture of son.The present inventor is based on foregoing discovery and completes the present invention.
Therefore, it is an object of the present invention to provide a kind of method for preparing halogenated butyl rubber.In the method, due to
Butyl rubber rubber solutions are carried out with halide reagent in the presence of the optionally water containing emulsifying agent so that in halogenated butyl rubber
Isomerization of the secondary bit architecture comprising secondary halogen atom to the primary bit architecture comprising primary halogen atom is effectively suppressed, so that
Gained halogenated butyl rubber has the primary bit architecture for including primary halogen atom of lower content, greatly reduces halogenated butyl rubber because different
Degraded caused by structure reaction.
It is a further object to provide the optionally water containing emulsifying agent by halogenating butyl rubber brewed brine fourth
The primary bit architecture comprising primary halogen atom in gained halogenated butyl rubber is reduced in base rubber and includes the Zhong Weijie of secondary halogen atom
Purposes in the mol ratio of structure.
Realizing the technical scheme of above-mentioned purpose of the present invention can be summarized as follows：
1. a kind of method for preparing halogenated butyl rubber, comprises the following steps：
A) solution comprising butyl rubber is reacted with halide reagent, obtain halogenated butyl rubber solution；And
B) the obtained halogenated butyl rubber solutions of step a) are post-processed, to reclaim halogenated butyl rubber,
Characterized in that, step a) halogenation is carried out in the presence of the optionally water containing emulsifying agent,
The primary bit architecture comprising primary halogen atom wherein in halogenated butyl rubber and the secondary bit architecture comprising secondary halogen atom
Mole ratio is not higher than 1:10, preferably no greater than 1:12, wherein following formula type III and II types represents to include the primary of primary halogen atom respectively
Bit architecture and the secondary bit architecture comprising secondary halogen atom：
In formula, X represents halogen, especially represents bromine.
2. according to the method for the 1st, the addition of its reclaimed water is based on the weight of the butyl rubber solution used in step a)
For 0.05-20 weight %, preferably 0.15-10 weight %, in particular 0.15-7 weight %.
3. according to the method for the 1st or 2, wherein emulsifying agent is selected from anionic, cationic, double type emulsifying agent and non-
Ionic emulsifying agent, cationic and nonionic emulsifier are preferably selected from, more preferably emulsifying agent is selected from alkylammonium salt, alkyl quaternary
Ammonium salt and its mixture.
4. according to the method for any one of 1-3 items, wherein for being used in forming step a) comprising butyl rubber
The solvent of solution is alkane or cycloalkane containing 5-15 carbon atom, for example, pentane, hexane, heptane, hexamethylene or it is mixed
Compound；And/or the gross weight of the solution based on butyl rubber, the content of butyl rubber is 5-30 weight %, and preferably 8-25 is heavy
Measure %, more preferably 8-12 weight %.
5. according to the method for any one of 1-4 items, wherein halide reagent is mol-chloric or molecular bromine, or in halogenation bar
Mol-chloric, the compound of molecular bromine, or any mixture of foregoing halide reagent are discharged under part, preferably using bromine.
6. according to the method for any one of 1-5 items, the wherein temperature of halogenation is not higher than 65 DEG C, preferably 20-60
℃；And/or the time of halogenation is usually 1-30 minutes, preferably 2-15 minutes, in particular 3-6 minutes.
7. according to the method for any one of 1-6 items, wherein butyl rubber is the copolymer of isobutene and isoprene, its
The total amount of all monomeric units of the amount of middle isoprene monomer unit based on butyl rubber is 0.5-3.0 moles of %.
8. according to the method for any one of 1-7 items, the wherein halogen quantity contained by halogenated butyl rubber is based on halobutyl
The gross weight of rubber is 0.5-3.0 weight %.
9. optionally the water containing emulsifying agent will in halogenating butyl rubber halogenated butyl rubber reduce obtained by halogenation fourth
The primary bit architecture comprising primary halogen atom in base rubber and the purposes in the mol ratio of the secondary bit architecture comprising secondary halogen atom, wherein
Following formula type III and II types represent the primary bit architecture comprising primary halogen atom and the secondary bit architecture comprising secondary halogen atom respectively：
In formula, X represents halogen, especially represents bromine,
Wherein the solution comprising butyl rubber reacts to obtain the halogenation of halogenated butyl rubber optional with halide reagent
Carried out in the presence of water of the ground containing emulsifying agent.
10. according to the purposes of the 9th, the primary bit architecture comprising primary halogen atom wherein in halogenated butyl rubber with comprising secondary
The mole ratio of the secondary bit architecture of halogen atom is not higher than 1:10, preferably no greater than 1:12.
11. according to the purposes of the 9th or 10, weight of the addition based on butyl rubber solution of its reclaimed water is 0.05-20
Weight %, preferably 0.15-10 weight %, in particular 0.15-7 weight %.
12. according to the purposes of any one of 9-11 items, wherein emulsifying agent is selected from anionic, cationic, double type
And nonionic emulsifier, cationic and nonionic emulsifier are preferably selected from, is more preferably selected from alkylammonium salt, quaternary ammonium alkyl
Salt and its mixture.
Embodiment
According to an aspect of the invention, there is provided a kind of method for preparing halogenated butyl rubber, comprises the following steps：
A) solution comprising butyl rubber is reacted with halide reagent, obtain halogenated butyl rubber solution；And
B) the obtained halogenated butyl rubber solutions of step a) are post-processed, to reclaim halogenated butyl rubber,
Characterized in that, step a) halogenation is carried out in the presence of the optionally water containing emulsifying agent,
The primary bit architecture comprising primary halogen atom wherein in halogenated butyl rubber and the secondary bit architecture comprising secondary halogen atom
Mole ratio is not higher than 1:10, wherein following formula type III and II types represents the primary bit architecture comprising primary halogen atom and comprising secondary respectively
The secondary bit architecture of halogen atom：
In formula, X represents halogen, especially represents bromine.
For the purpose of the present invention, butyl rubber is the copolymer that isobutene forms with a small amount of isoprene copolymer.Based on butyl
The total amount of all monomeric units of rubber, the content of isoprene monomer unit is usually 0.5-3.0 moles of % in butyl rubber.
In the present invention, had no particular limits for the molecular weight of butyl rubber, as long as the butyl rubber can be carried out
Halogenation introduces halogen atom.Typically, the weight average molecular weight of butyl rubber is 30 × 104-100×104。
The butyl rubber used as the present invention, both commercially available acquisition, such as the production of Co., Ltd of Sinopec
Yanshan IIR1751, it can also be prepared by the known method of this area.
In order to which butyl rubber is carried out into halogenation to introduce halogen atom so as to be modified to it, generally butyl rubber is dissolved in
Contacted in solvent in the form of butyl rubber solution with halide reagent.The principle that solvent is selected is not influence butyl rubber
Halogenation, nor affect on the structure of halogenating butyl rubber product.On the other hand, the solvent for suitably forming the solution can be alkane
Hydrocarbon, cycloalkane, aromatic hydrocarbons, halogenated hydrocarbons or its mixture.Advantageously, using nonpolar inertia alkane and cycloalkane, especially
Alkane or cycloalkane containing 5-15 carbon atom, such as pentane, hexane, heptane, hexamethylene or its mixture etc..
The concentration of butyl rubber solution is conventional, as long as halogenation can be carried out.Typically, based on butyl rubber
The gross weight of sol solution, the content of the butyl rubber in butyl rubber solution are 5-30 weight %, preferably 8-25 weight %, more
Preferably 8-12 weight %.
In order to realize the object of the invention, the halogenation of butyl rubber solution and halide reagent is needed optionally containing emulsification
Carried out in the presence of the water of agent.Inventor has found that the presence of water can be obvious in the research process reacted halogenating butyl rubber
The content of the primary bit architecture of primary halogen atom is included during reduction halogenation in halogenated butyl rubber.
Pair it is advantageous in the present invention that the weight of butyl rubber solution that the addition of water is based on using in step a) is
0.05-20 weight %, preferably 0.15-10 weight %, in particular 0.15-7 weight %.The dosage of water does not have due very little
Effect；The dosage of water is too many, and aqueous phase easily forms continuous phase, and material system is very unstable in tubular reactor.
The dosage of emulsifying agent should generally allow the water to be emulsified in the butyl rubber solution used in step a), or emulsification
In halogenation mixture in step a), so as to realize being uniformly distributed for water.
Water can add before halogenation, such as be added in butyl rubber solution, can also be in halogenation process
In be added in halogenation mixture.Preferably, connect again with halide reagent after adding water in butyl rubber solution
Touch.Because water and butyl rubber solution are mutual exclusive two systems, after introducing water in rubber solutions, oil water two phase system
It is not easy to be well mixed, this can suppress the effect for introducing water, especially in the case of water is less.Therefore, in water or reacting
Emulsifying agent is introduced in mixture can be effectively prevented from profit layering, so as to give full play to water to suppressing primary in halogenated butyl rubber
Bit architecture rise, the effect of product degraded.Therefore, it is according to the present invention advantageous that step a) halogenation is containing emulsifying agent
Water in the presence of carry out.
Emulsifying agent can be selected from anionic, cationic, double type and nonionic emulsifier, preferred cationic type
And nonionic emulsifier.Anionic emulsifier includes potassium oleate, enuatrol, odium stearate, neopelex, ten
Dialkyl sulfonates, dioctyl sodium sulfosuccinate etc..Cationic emulsifier includes alkylammonium salt, alkyl quaternary ammonium salts, such as
Lauryl ammonium chloride, dimethyl hexadecyl base ammonium bromide, cetyl trimethylammonium bromide, dimethyl hexadecyl base chlorination
Ammonium, hexadecyltrimethylammonium chloride etc..Double type emulsifying agent includes double dodecyloxy bis phosphoric acid sodium, double (cetyls
Alkyl dimethyl ammonium chloride) etc..Nonionic emulsifier includes polyethylene glycol oxide Arrcostab, polyalcohol Arrcostab, polyethylene glycol oxide
Polyalcohol Arrcostab, polyethylene oxide alkyl ethers, polyethylene glycol oxide alkyl aryl ether, polyalcohol cyclic ethers, alkylolamides, polyoxygenated
Vinyl alkyl acid amides etc., and their mixture, as sorbitan monooleate, sorbitan monostearate,
Polyoxyethylene 20 sorbitan monooleate, polyoxyethylene 20 sorbitan monostearate.But in general, anionic
Emulsifying agent such as alkyl carboxylic acid salt, alkyl sulfonates, alkylsurfuric acid salt, alkyl phosphoric acid salt etc. are less preferably adapted for this hair
Bright, because this kind of emulsifying agent can react during halogenation with halogen acids such as HBr, the organic acid of generation easily remains in production
In product, the performance of product is adversely affected.
Emulsifying agent can first be added to the water, and then add the water comprising emulsifying agent in the solution of butyl rubber, or will
Water comprising emulsifying agent is added in the reactant mixture comprising butyl rubber solution and halide reagent.Emulsifying agent is independently of water
It is individually added into any order in the solution of butyl rubber with water, or emulsifying agent is individually added into comprising fourth in any order with water
In the reactant mixture of base rubber solutions and halide reagent.
It is conventional to carry out the halide reagent that halogenation uses in step a).Halide reagent can be mol-chloric or molecule
Bromine, or to discharge mol-chloric, the compound of molecular bromine, or any mixture of foregoing halide reagent under halogenation conditions, it is excellent
Choosing uses bromine.Halide reagent can be used directly, be used after can also being configured to solution.
In order to carry out the halogenation in step a), butyl rubber solution is generally set to be deposited in the optionally water containing emulsifying agent
Contacted lower with halide reagent.Such as can be by by butyl rubber solution, water and optional emulsifying agent or will be aqueous and optional
The butyl rubber solution of emulsifying agent is well mixed with halide reagent, and a period of time is then kept at a temperature of halogenation.
Depending on halide reagent, halogenation can be carried out in wide temperature range.Advantageously, halogenation is usual
It can carry out at a temperature of not higher than 65 DEG C, preferably be carried out at 20 DEG C -60 DEG C.The halogenation time depends on being reached
Halogenation degree, typically no more than 20 minutes, preferably 2-15 minutes, in particular 3-6 minutes.
After step a) halogenation is completed, halogenated butyl rubber solution is obtained, by the halogenated butyl rubber solution
Post-processed, to reclaim halogenated butyl rubber, that is, obtain halogenated butyl rubber product.Can be in a variety of ways from halobutyl rubber
Halogenated butyl rubber is reclaimed in sol solution.Nertralizer is first generally added into halogenated butyl rubber solution, to neutralize halogen acids
Accessory substance.Any chemical reagent for carrying out the neutralization purpose can be used.Nertralizer is usually alkaline aqueous solution.Suitable alkali
Property the aqueous solution can be following alkaline matter the aqueous solution：Alkali metal hydroxide, particularly sodium hydroxide, potassium hydroxide, hydrogen
Amine-oxides, alkali carbonate, alkali metal hydrogencarbonate, ammonium carbonate, ammonium hydrogen carbonate, or their any mixture.Neutralize
The dosage of agent should be enough the hydrogen halide by-product for neutralizing halogenation formation.After by-product hydrogen halide is neutralized, favorably
Be that other auxiliary agents can be added into the halogenated butyl rubber solution so obtained, such as stabilizer such as epoxidized soybean oil, sulphur
Change speed regulator such as calcium stearate, antioxidant etc..Finally remove the volatilizations such as solvent and the water in halogenated butyl rubber solution
Property composition, obtains halogenated butyl rubber product.
In the halogenated butyl rubber obtained according to the inventive method, the primary bit architecture therein comprising primary halogen atom and bag
The mole ratio of secondary bit architecture containing secondary halogen atom is not higher than 1:10, preferably no greater than 1:12, wherein following formula type III and II types point
The primary bit architecture comprising primary halogen atom that Biao Shi be in halogenated butyl rubber and the secondary bit architecture comprising secondary halogen atom：
In formula, X represents halogen, especially represents bromine.
In the halogenated butyl rubber obtained according to the inventive method, the halogen quantity included in the halogenated butyl rubber is based on
The gross weight of halogenated butyl rubber is usually 0.5-3.0 weight %.
Compared to conventional method --- what the halogenation method carried out in the presence of anhydrous obtained has higher proportion (usually more than
10 moles of % (uncle position/(uncle position+secondary position))) primary bit architecture halogenated butyl rubber, the halobutyl that the inventive method obtains
Rubber has the primary bit architecture for including primary halogen atom of minor proportion, and therefore, halogenation causes the palliating degradation degree of butyl rubber
Reduce.
Therefore, according to another aspect of the present invention, there is provided optionally the water containing emulsifying agent is by halogenating butyl rubber
The primary bit architecture comprising primary halogen atom in gained halogenated butyl rubber is reduced in halogenated butyl rubber processed and includes secondary halogen atom
Secondary bit architecture mol ratio in purposes, wherein following formula type III and II types represent to include the primary bit architecture of primary halogen atom respectively
With the secondary bit architecture comprising secondary halogen atom：
In formula, X represents halogen, especially represents bromine,
Wherein the solution comprising butyl rubber reacts to obtain the halogenation of halogenated butyl rubber optional with halide reagent
Carried out in the presence of water of the ground containing emulsifying agent.
The restriction and description for all technical characteristics being related in purposes of the present invention are applicable the present invention and prepare halogenated butyl rubber
The restriction and description of character pair in method.
In the preferred embodiment according to purposes of the present invention, include primary halogen atom primary in gained halogenated butyl rubber
The mole ratio of bit architecture and the secondary bit architecture comprising secondary halogen atom is not higher than 1:10, preferably no greater than 1:12.
In another preferred embodiment according to purposes of the present invention, weight of the addition based on butyl rubber solution of water
For 0.05-20 weight %, preferably 0.15-10 weight %, in particular 0.15-7 weight %.
In the still another embodiment according to purposes of the present invention, emulsifying agent is selected from anionic, cationic, Shuangzi
Type emulsifying agent and nonionic emulsifier, are preferably selected from cationic and nonionic emulsifier, be more preferably selected from alkylammonium salt,
Alkyl quaternary ammonium salts and its mixture.
Embodiment
In following embodiment and comparative example, the structural characterization of halogenated butyl rubber uses Bruker companies of Switzerland
AVANCE400MHz NMR spectra instrument, the tesla of magnetic field intensity 9.40, sample pipe diameter 5mm, sample is at normal temperatures with deuterated chlorine
It is imitative to dissolve the solution for being configured to mass content 2%, using TMS as internal standard, test at room temperature.
The molecular weight of halogenated butyl rubber is determined using Britain PL-220 type liquid phase gel permeation chromatography (GPC) instrument, wherein
Mobile phase is THF, flow velocity 0.7ml/min, solution concentration 0.6mg/ml, and the μ l of sample size 200, test temperature is 35 DEG C.Mark
Quasi- polystyrene is corrected curve determination, is calculated using butyl rubber K, α value：K=8.5 × 10-5, α=0.75.
Auxiliary agent such as stearic acid, calcium stearate analysis in polymer carries out infrared spectrum analysis test, instrument using coating method
Device is selected from Nicolet560 type Fourier transformation infrared spectrometers.It is solvent from carbon disulfide, sample is made into 45-55mg/
Ml concentrated solution, then by solution on KBr chip direct film, stand 4 minutes, make solvent volatilize after carry out infrared light
Spectrum test.Scanning 32 times, resolution ratio 4cm-1。
Reference example
As without particularly pointing out, the butyl rubber solution used in embodiments below and comparative example is matched somebody with somebody as follows
System：Taking butyl rubber, (Yansan IIR1751, (degree of unsaturation is 1.7 moles of % to the production of Co., Ltd of Sinopec, door
Buddhist nun's viscosity is 51, and weight average molecular weight is 46.8 × 104) it is dissolved in n-hexane to obtain a solution.The solution left standstill is taken 2/ after 1 week
3 upper strata glue, the glue of lower floor 1/3 are abandoned.Butyl rubber containing 10 weight % in the upper strata glue, the glue conduct
Butyl rubber solution is standby.
Embodiment 1 (contrast)
400g butyl rubber solutions are placed in 1L three-necked flasks, measured value is the water content of the solution by weight
65ppm.The solution is warming up to after 30 DEG C the addition 1.6g bromines under the conditions of lucifuge, quick stirring stands 4.5 minutes after 30 seconds.
Then 0.2mol/L NaOH aqueous solution 60ml are added, after continuing stirring 5 minutes, after low-pressure steam removes most of solvent again
Moisture and residual solvent are removed in 110 DEG C of two-roll mills, obtains brombutyl product.The structure of products obtained therefrom, contain
Amount the results are shown in Table 1.
Embodiment 2 (contrast)
400g butyl rubber solutions are placed in 1L three-necked flasks.It is 5% that 0.32g mass contents are added in the solution
Dimethyl hexadecyl bromide aqueous ammonium (solution is hereinafter referred to as aqueous emulsion), gained glue water content are real by weight
Measured value is 815ppm.30 DEG C are warming up to after stirring, 1.6g bromines are added under the conditions of lucifuge, quick stirring is stood after 30 seconds
4.5 minute.Then 0.2mol/L NaOH aqueous solution 60ml are added, after continuing stirring 5 minutes, are removed through low-pressure steam most of
Remove moisture and residual solvent after solvent in 110 DEG C of two-roll mills again, obtain brombutyl product.Products obtained therefrom
Structure, content results are shown in Table 1.
Embodiment 3~6
For experimentation with embodiment 2, the aqueous emulsion amount simply added is different.Detailed aqueous emulsion addition and
Bromination the results are shown in Table 1.
Table 1
Note：aIt is 65ppm to survey glue water content value；bIt is 815ppm to survey glue water content value.
* " uncle position " represents the primary bit architecture that primary halogen atom is included in halogenated butyl rubber, and " secondary position " represents halobutyl rubber
The secondary bit architecture of secondary halogen atom is included in glue.
In terms of the result of table 1, halogenating butyl rubber reaction carry out can obviously reduce in the presence of aqueous emulsion uncle position/
(uncle position+secondary position) molar ratio.Meanwhile the presence of aqueous emulsion can also suppress the drop of brombutyl molecular weight of product
It is low, that is to say, that to suppress the degraded of brombutyl product.
Embodiment 7
400g butyl rubber solutions are placed in 1L three-necked flasks.0.60g is added in the solution and is free of any emulsifying agent
Distilled water, the water content of gained glue is 0.15% by weight.30 DEG C are warming up to after stirring, is added under the conditions of lucifuge
Enter 1.6g bromines, quick stirring stands 4.5 minutes after 30 seconds.Then 0.2mol/L NaOH aqueous solution 60ml are added, continue to stir
After mixing 5 minutes, moisture and residual solvent are removed in 110 DEG C of two-roll mills again after low-pressure steam removes most of solvent,
Obtain brombutyl product.Take three pieces of small samples at random in gained sample, its primary bit architecture content is shown in Table 2.Meanwhile
Three pieces of small samples are taken at random to the halogenated butyl rubber product that embodiment 3 obtains, its primary bit architecture content is shown in Table 2.
Table 2
* " uncles position " represents the primary bit architecture that primary halogen atom is included in halogenated butyl rubber, and " secondary position " represents halobutyl rubber
The secondary bit architecture of secondary halogen atom is included in glue.
In terms of the result of table 2, compared to three chance samples in embodiment 3, three samples of grab sample in embodiment 7
Average uncle position/secondary position mol ratio of product is although relatively low, and about 1:10, but fluctuate obvious.This shows that the introducing of emulsifying agent helps
In giving full play to effect of the water in uncle position/(uncle position+secondary position) mol ratio for reducing halogenated butyl rubber, the steady of product quality is improved
Qualitative and homogeneity.
Embodiment 8
400g butyl rubber solutions are placed in 1L three-necked flasks.2.4g distilled water and 0.24g is added in the solution
Odium stearate, gained glue water content is by weight 0.6%, and content of the odium stearate in rubber be by weight
0.6%.30 DEG C are warming up to after stirring, 1.6g bromines are added under the conditions of lucifuge, quick stirring stands 4.5 points after 30 seconds
Clock.Then 0.2mol/L NaOH aqueous solution 60ml are added, after continuing stirring 5 minutes, most of solvent is removed through low-pressure steam
Remove moisture and residual solvent in 110 DEG C of two-roll mills again afterwards, obtain brombutyl product.
The molar percentage of the uncle position of gained brombutyl product/(uncle position+secondary position) is 3.62%, while bromination fourth
Stearic acid content is 0.3 weight % in base rubber product.As can be seen here, because of the emulsifying agent odium stearate and butyl rubber bromine of addition
The stearic acid changed the accessory substance HBr reactions of reaction generation and generated is not fully neutralized, and some remains on bromination
In butyl rubber product.
Claims (31)
1. a kind of method for preparing halogenated butyl rubber, comprises the following steps：
A) solution comprising butyl rubber is reacted with halide reagent, obtain halogenated butyl rubber solution；And
B) the obtained halogenated butyl rubber solutions of step a) are post-processed, to reclaim halogenated butyl rubber,
Characterized in that, step a) halogenation is carried out in the presence of the water containing emulsifying agent, the emulsifying agent is selected from quaternary ammonium alkyl
Salt,
Mole of the primary bit architecture comprising primary halogen atom and the secondary bit architecture comprising secondary halogen atom wherein in halogenated butyl rubber
Amount is than being not higher than 1:10, wherein following formula type III and II types represents the primary bit architecture comprising primary halogen atom and comprising secondary halogen original respectively
The secondary bit architecture of son：
In formula, X represents halogen.
2. the primary bit architecture comprising primary halogen atom in method according to claim 1, wherein halogenated butyl rubber with comprising secondary
The mole ratio of the secondary bit architecture of halogen atom is not higher than 1:12.
3. method according to claim 1, wherein X represent bromine.
4. method according to claim 1, the addition of its reclaimed water is based on the weight of the butyl rubber solution used in step a)
For 0.05-20 weight %.
5. method according to claim 1, the addition of its reclaimed water is based on the weight of the butyl rubber solution used in step a)
For 0.15-10 weight %.
6. method according to claim 1, the addition of its reclaimed water is based on the weight of the butyl rubber solution used in step a)
For 0.15-7 weight %.
7. method as claimed in one of claims 1-6, wherein emulsifying agent are selected from lauryl ammonium chloride, dimethyl hexadecyl
Base ammonium bromide, cetyl trimethylammonium bromide, dimethyl hexadecyl ammonium chloride and hexadecyltrimethylammonium chloride.
8. method as claimed in one of claims 1-6, wherein for being used in forming step a) comprising butyl rubber
The solvent of solution is non-polar solven.
9. method as claimed in one of claims 1-6, wherein for being used in forming step a) comprising butyl rubber
The solvent of solution is the alkane containing 5-15 carbon atom.
10. method as claimed in one of claims 1-6, wherein for being used in forming step a) comprising butyl rubber
The solvent of solution is the cycloalkane containing 5-15 carbon atom.
11. method as claimed in one of claims 1-6, wherein for being used in forming step a) comprising butyl rubber
The solvent of solution is pentane, hexane, heptane, hexamethylene or its mixture.
12. method as claimed in one of claims 1-6, wherein the gross weight of the solution based on butyl rubber, butyl rubber
Content be 5-30 weight %.
13. method as claimed in one of claims 1-6, wherein the gross weight of the solution based on butyl rubber, butyl rubber
Content be 8-25 weight %.
14. method as claimed in one of claims 1-6, wherein the gross weight of the solution based on butyl rubber, butyl rubber
Content be 8-12 weight %.
15. according to any one of claim 1,2 and 4-6 method, wherein halide reagent is mol-chloric or molecular bromine, or for
Mol-chloric, the compound of molecular bromine, or any mixture of foregoing halide reagent are discharged under halogenation conditions.
16. method as claimed in one of claims 1-6, wherein halide reagent are bromine.
17. the temperature of method as claimed in one of claims 1-6, wherein halogenation is not higher than 65 DEG C.
18. the temperature of method as claimed in one of claims 1-6, wherein halogenation is 20-60 DEG C.
19. the time of method as claimed in one of claims 1-6, wherein halogenation is 1-30 minutes.
20. the time of method as claimed in one of claims 1-6, wherein halogenation is 2-15 minutes.
21. the time of method as claimed in one of claims 1-6, wherein halogenation is 3-6 minutes.
22. method as claimed in one of claims 1-6, wherein butyl rubber are the copolymer of isobutene and isoprene,
Wherein the total amount of all monomeric units of the amount of isoprene monomer unit based on butyl rubber is 0.5-3.0 moles of %.
23. the halogen quantity contained by method as claimed in one of claims 1-6, wherein halogenated butyl rubber is based on halobutyl
The gross weight of rubber is 0.5-3.0 weight %.
24. the water containing emulsifying agent is in halogenated butyl rubber obtained by being reduced in halogenating butyl rubber halogenated butyl rubber
Primary bit architecture comprising primary halogen atom and the purposes in the mol ratio of the secondary bit architecture comprising secondary halogen atom, wherein following formula type III
Represent the primary bit architecture comprising primary halogen atom and the secondary bit architecture comprising secondary halogen atom respectively with II types：
In formula, X represents halogen,
Wherein the solution comprising butyl rubber reacts to obtain the halogenation of halogenated butyl rubber containing emulsification with halide reagent
Carried out in the presence of the water of agent, the emulsifying agent is selected from alkyl quaternary ammonium salts.
25. purposes according to claim 24, wherein X represent bromine.
26. the primary bit architecture comprising primary halogen atom in purposes according to claim 24, wherein halogenated butyl rubber with comprising
The mole ratio of the secondary bit architecture of secondary halogen atom is not higher than 1:10.
27. the primary bit architecture comprising primary halogen atom in purposes according to claim 24, wherein halogenated butyl rubber with comprising
The mole ratio of the secondary bit architecture of secondary halogen atom is not higher than 1:12.
28. according to any one of claim 24-27 purposes, weight of the addition based on butyl rubber solution of its reclaimed water is
0.05-20 weight %.
29. according to any one of claim 24-27 purposes, weight of the addition based on butyl rubber solution of its reclaimed water is
0.15-10 weight %.
30. according to any one of claim 24-27 purposes, weight of the addition based on butyl rubber solution of its reclaimed water is
0.15-7 weight %.
31. according to any one of claim 24-27 purposes, wherein emulsifying agent is selected from lauryl ammonium chloride, dimethyl ten
Six alkyl bromination ammoniums, cetyl trimethylammonium bromide, dimethyl hexadecyl ammonium chloride, hexadecyltrimethylammonium chloride.
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| CN113307987A (en) * | 2016-07-25 | 2021-08-27 | 西南科技大学 | Preparation method of brominated butyl rubber latex |
| JP7132941B2 (en) * | 2017-04-12 | 2022-09-07 | リライアンス、インダストリーズ、リミテッド | Preparation process of halogenated butyl rubber |
| CN109535450B (en) * | 2018-11-20 | 2021-06-25 | 山东京博中聚新材料有限公司 | Butyl rubber solution, preparation method and preparation device thereof |
| CN110294812B (en) * | 2019-07-05 | 2022-04-22 | 黄河三角洲京博化工研究院有限公司 | Chlorinated butyl rubber and preparation process thereof |
| CN110229254B (en) * | 2019-07-05 | 2022-04-22 | 黄河三角洲京博化工研究院有限公司 | Bromination method of butyl rubber and brominated butyl rubber |
| CN111303328A (en) * | 2020-03-31 | 2020-06-19 | 浙江信汇新材料股份有限公司 | Deacidifying method for butyl rubber halogenation reaction product |
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| CN1225649A (en) * | 1996-07-24 | 1999-08-11 | 埃克森化学专利公司 | Improved process for halogenating isomonoolefin copolymers |
| CN103467635A (en) * | 2013-08-30 | 2013-12-25 | 清华大学 | Method of controlling halogen substitution site in halogenated butyl rubber |
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| CN1225649A (en) * | 1996-07-24 | 1999-08-11 | 埃克森化学专利公司 | Improved process for halogenating isomonoolefin copolymers |
| CN103467635A (en) * | 2013-08-30 | 2013-12-25 | 清华大学 | Method of controlling halogen substitution site in halogenated butyl rubber |
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